EP0110377B1 - Dehydrohalogenierungsverfahren - Google Patents

Dehydrohalogenierungsverfahren Download PDF

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Publication number
EP0110377B1
EP0110377B1 EP83111953A EP83111953A EP0110377B1 EP 0110377 B1 EP0110377 B1 EP 0110377B1 EP 83111953 A EP83111953 A EP 83111953A EP 83111953 A EP83111953 A EP 83111953A EP 0110377 B1 EP0110377 B1 EP 0110377B1
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EP
European Patent Office
Prior art keywords
reactor
alkali
catalyst
aqueous alkali
halogenated hydrocarbon
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EP83111953A
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English (en)
French (fr)
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EP0110377A1 (de
Inventor
Louis Joseph Maurin Iii
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons

Definitions

  • This invention relates to an improvement in the process for dehydrohalogenating a halogenated hydrocarbon to an ethylenically unsaturated product in the presence of a phase-transfer catalyst.
  • phase-transfer catalysis describes reactions between reactants located in different phases brought about by the use of small quantities of an agent which transfers one reactant across the interface into the other phase so that the reaction can proceed.
  • the phase-transfer agent is not consumed but performs the transport function repeatedly. See Starks, J. Am. Chem. Soc. 93:1, 195 (1971) and Starks et al. J. Am. Chem. Soc. 95:11, 3613 (1973). Also see U.S. 3,992,432 (to Napier et al.) and a book by Starks et al, entitled “Phase-Transfer Catalysis", Academic Press, New York, N.Y. 1978.
  • the first paper in the above series considers organic-soluble quaternary ammonium and phosphonium ions to be excellent agents for the transport of anions from aqueous phase to an organic phase.
  • Such quaternary ions thus are effective phase-transfer catalysts in reactions in which anions participate, for example, in displacement reactions.
  • a typical catalytic dehydrohalogenation process is described in U.S. Patent 3,981,937 to Campbell et al., wherein 3,4-dichlorobutene-1 (sometimes hereafter abbreviated to DCB) is dehydrochlorinated with aqueous alkali to 2-chlorobutadiene-1,3 (also known as chloroprene).
  • the catalyst is a quaternary ammonium chloride but can also be another phase-transfer catalyst; see, for example, U.S. 3,639,492, 3,639,493, and 3,876,716 (all to Campbell).
  • the dehydrochlorination is often carried out in a series of continuous stirred-tank reactors, the initial stages being cooled to remove the heat of the reaction.
  • DCB, the catalyst, and an excess of aqueous NaOH are fed into the first reactor, where much of the reaction takes place.
  • the reaction rate decreases, so that a large proportion of the total reactor volume is required to complete the last few percent of the reaction.
  • Crude chloroprene is recovered from the effluent of the last stage; aqueous and organic phases are separated, and waste organics and waste brine are disposed of.
  • Any saturated or unsaturated halogenated hydrocarbon which can be dehydrohalogenated with aqueous alkali in the presence of a phase-transfer catalyst is a suitable starting material in the process of this invention. Particularly important are 1,2,3,4-tetrachlorobutane, 3,4-dichlorobutene-1, and 2,3,4-trichlorobutene-1.
  • Other starting halogenated hydrocarbons include, for example, 2,3-dichlorobutane, 2-bromoethylbenzene, 1,2-dichloroethane, 1,2-dibromoethane, and chlorocyclohexane.
  • Each of R', R 2 , and R 3 groups in these quaternary ammonium chlorides may also contain a hydroxyl or ether group in a position beta to the nitrogen atom.
  • the amount of the quaternary ammonium compound is about 0.01-10% by weight of the starting halogenated hydrocarbon.
  • phase-transfer catalysts include quaternary phosphonium salts and sulfonium salts having their respective formulas R'R 2 R 3 R 4 PX and R'R z R 3 SX in which X is the anion, and R 1 , R 2 , R 3 , and R 4 have the same meaning as above.
  • the alkali can be any alkali, such as sodium hyydroxide, potassium hydroxide, or calcium hydroxide, but usually will be sodium hydroxide.
  • the alkali normally will be used in slight excess, and the usual mole ratio of alkali to DCB will be approximately 1.001 to 1.3, but this ratio is not critical.
  • reactors stages employed in the process of this invention are two, a larger number may be preferred.
  • the reactors preferably are made of or lined with a corrosion-resistant material, such as, for example, nickel. They are provided with adequate heating and cooling means and with an agitating means.
  • Figs. 2 and 3 The improved process of the present invention can be well understood by comparing Figs. 2 and 3 with Fig. 1.
  • a conventional prior art process represented by Fig. 1, the dehydrohalogenation is carried out in several stages, which are here shown as reactors R1, R2 and R3.
  • a mixture of catalyst with the starting halogenated hydrocarbon is fed to R1 through line 1, and aqueous alkali is fed through line 2.
  • the effluent from each stage is fed to the next stage, and the effluent from the last stage is separated into the organic phase and the aqueous phase in decanter D.
  • the ethylenically unsaturated product is recovered from the organic phase removed through line 3, and waste brine is removed through line 4.
  • a mixture of catalyst with the halogenated hydrocarbon for example DCB
  • a mixture of catalyst with the halogenated hydrocarbon for example DCB
  • Fresh aqueous alkali solution is fed to reactor R2 through line 20.
  • the effluent from R2 is introduced to reactor R3, and the effluent from R3 is separated into phases in decanter D2.
  • the ethylenically unsaturated product for example, chloroprene, is recovered from the organic phase, which is removed through line 30, while the aqueous phase containing a mixture of sodium hydroxide and sodium chloride is fed through line 50 to the first stage.
  • the effluent from R1 is separated in decanter D1 into the organic phase containing in the exemplary case a mixture of DCB and chloroprene and the aqueous phase, which is waste brine.
  • the organic phase is fed through line 60 to stage R2, and waste brine is removed through line 40.
  • Fig. 3 shows schematically a two-reactor process of the present invention.
  • a mixture of catalyst with the halogenated hydrocarbon is fed through line 100 to the first stage, R1.
  • Fresh aqueous alkali solution fed through line 200 is combined in line 600 with the upper phase from decanter D1 containing a mixture of unchanged starting halogenated hydrocarbon (e.g., DCB) and ethylenically unsaturated product (e.g., chloroprene).
  • the combined two-phase mixture is introduced into reactor R2, and the effluent from reactor R2 is separated into phases in decanter D2.
  • fresh aqueous alkali solution can be fed directly to reactor R2 in the manner shown in Fig. 2.
  • the organic phase which is removed through line 300, contains mainly the ethylenically unsaturated product.
  • the aqueous phase consisting of a mixture of alkali metal hydroxide and brine, is fed to reactor 1 via line 500.
  • the process of the present invention results in a higher conversion of halogenated hydrocarbon to ethylenically unsaturated product than does the conventional process.
  • less catalyst and alkali are required than in the conventional process because the reaction driving forces are spread more evenly throughout the existing reactor volumes, thus resulting in considerable savings.
  • These improvements are obtained for any number of reactors arranged in series.
  • the preferred location of fresh alkali feed is about the midpoint of the reactor train; however, most of the benefits of this invention will also be realized when the fresh alkali solution is fed to some other stage between the first reactor and the last. Except for the relocation of the various feed and recovery streams, and reduction in alkali and catalyst flows, other process conditions, such as the temperature and flow rates, are substantially the same as in the past.
  • run A was made according to the prior art process shown in Fig. 1, while run B was made according to the present process.
  • three back-mixed 1650 mL nickel reactors were used.
  • DCB containing 2500 ppm of catalyst, cocobenzylbis((3-hydroxypropyl)ammonium chloride was fed to the first stage at a rate of 0.918 kg/hr.
  • Fresh aqueous alkali was a 22% solution of NaOH in water.
  • the feed mole ratio of NaOH to DCB was 1.058; in run B, the ratio was 1.064.
  • the DCB conversion in each stage was determined for each run by gas chromatography. The results are shown in the following table:
  • This example is a process simulation for a plant-size operation based on known reaction kinetics and on the use of known equipment. The operating parameters as well as the results were calculated for a process employing eight back-mixed, liquid-full reactors connected in series.
  • the catalyst is the same as in Example 1, and the DCB feed rate is 16,589 kg/hr.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (8)

1. Verfahren zur Dehydrohalogenierung eines halogenierten Kohlenwasserstoffs zu einem ethylenisch ungesättigten Produkt mit wässrigem Alkali in Gegenwart eines Phasentransferkatalysators in einer Reihe von mindestens zwei, voll mit Flüssigkeit gefüllten Reaktoren, die in einer Kaskadenanordnung arbeiten, wobei die Verbesserung darin besteht, daß der halogenierte Kohlenwasserstoff und der Katalysator in den ersten Reaktor eingespeist werden, während frisches wässriges Alkali in einen Reaktor hinter dem ersten Reaktor eingespeist wird, wobei das Alkali zusammen mit der organischen Phase, die in diesen Reaktor eintritt, eingespeist werden kann, der Abfluß von letztem Reaktor getrennt wird in eine teilweise verbrauchte wässrige Alkalilösung, die in den ersten Reaktor eingespeist wird, und eine organischen Phase, aus welcher das ethylenisch ungesättigte Produkt gewonnen wird, und Abfall-Salzlösung aus dem Abfluß von dem Reaktor, der unmittelbar vor dem Einspeisepunkt für das frische wässrige Alkali liegt, entfernt wird.
2. Verfahren nach Anspruch 1, worin der als Ausgangsverbindung eingesetzte halogenierte Kohlenwasserstoff 1,2,3,4-Tetrachlorbutan oder 3,4-Dichlorbuten-1 ist.
3. Verfahren nach Anspruch 1, worin der Katalysator eine quaternäre Ammoniumverbindung ist.
4. Verfahren nach Anspruch 3, worin der Katalysator ein quaternäres Ammoniumchlorid ist.
5. Verfahren nach Anspruch 4, worin das quaternäre Ammoniumchlorid die Formel R1R2R3R4NCl besitzt, worin jeder der Reste R', R2 und R3 unabhängig ein C1-C20-Alkyl-, ein C2-C20-Alkenyl- oder ein C7-C20-Aralkylrest ist, und R4 ein C6-C20-Alkyl- oder -Alkenyl-, Benzyl- oder ein (C6-C20)-Alkyl- oder -Alkenyl-substituierter Benzylrest ist, mit der Maßgabe, daß jeder der Reste R1, R2 und R3 auch einen Hydroxyl- oder Etherrest in einer Position in β-Stellung zu dem Stickstoffatom enthalten kann.
6. Verfahren nach Anspruch 1, worin die Anzahl der Reaktoren 3 bis 8 beträgt.
7. Verfahren nach Anspruch 1, worin das Alkali Natriumhydroxid ist.
8. Verfahren nach Anspruch 1, worin der Ort der frischen Alkalizuspeisung etwa die Mitte des Reaktorzuges ist.
EP83111953A 1982-11-29 1983-11-29 Dehydrohalogenierungsverfahren Expired EP0110377B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US445155 1982-11-29
US06/445,155 US4418232A (en) 1982-11-29 1982-11-29 Dehydrohalogenation process

Publications (2)

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EP0110377A1 EP0110377A1 (de) 1984-06-13
EP0110377B1 true EP0110377B1 (de) 1985-10-30

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EP83111953A Expired EP0110377B1 (de) 1982-11-29 1983-11-29 Dehydrohalogenierungsverfahren

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US (1) US4418232A (de)
EP (1) EP0110377B1 (de)
JP (1) JPS59108727A (de)
CA (1) CA1207803A (de)
DE (1) DE3361129D1 (de)
SU (1) SU1277888A3 (de)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62148441A (ja) * 1985-12-23 1987-07-02 Mitsui Toatsu Chem Inc アルケニルフェノ−ルの製造方法
US5237114A (en) * 1992-03-20 1993-08-17 E. I. Du Pont De Nemours And Company Removal of catalyst from chloroprene by treatment with oxy acid
EP0677503B1 (de) * 1992-12-29 1999-04-07 Daikin Industries, Limited Verfahren zur herstellung von 1,1,1,3,3-pentafluoropropan
US5396002A (en) * 1993-08-18 1995-03-07 The Dow Chemical Company Process to produce vinylidene chloride using phase transfer catalyst
US6380446B1 (en) 2000-08-17 2002-04-30 Dupont Dow Elastomers, L.L.C. Process for dehydrohalogenation of halogenated compounds
ITMI20052455A1 (it) * 2005-12-22 2007-06-23 Solvay Solexis Spa Procedimento per la preparazione di fluoroalogenoeteri
ITMI20052456A1 (it) * 2005-12-22 2007-06-23 Solvay Solexis Spa Procedimento per la preparazione di fluoroalogenoeteri
JP2010229092A (ja) * 2009-03-27 2010-10-14 Tokuyama Corp トリクロロプロペンの製造方法
US8969645B2 (en) * 2012-12-14 2015-03-03 Chevron U.S.A. Inc. Process for reducing chloride in hydrocarbon products using an ionic liquid catalyst
WO2015166962A1 (ja) * 2014-04-28 2015-11-05 ダイキン工業株式会社 組成物
JP5987926B2 (ja) * 2014-04-28 2016-09-07 ダイキン工業株式会社 組成物

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981937A (en) * 1966-06-03 1976-09-21 E. I. Du Pont De Nemours And Company Dehydrohalogenation of 3,4-dichloro-1-butene
US3754044A (en) * 1968-02-28 1973-08-21 Du Pont Dehydrohalogenation of halogenated compounds

Also Published As

Publication number Publication date
JPH0146496B2 (de) 1989-10-09
JPS59108727A (ja) 1984-06-23
SU1277888A3 (ru) 1986-12-15
EP0110377A1 (de) 1984-06-13
US4418232A (en) 1983-11-29
DE3361129D1 (en) 1985-12-05
CA1207803A (en) 1986-07-15

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